Assessment of the technological viability of photoelectrochemical devices for oxygen and fuel production on Moon and Mars.

Human deep space exploration is presented with multiple challenges, such as the reliable, efficient and sustainable operation of life support systems. The production and recycling of oxygen, carbon dioxide (CO2) and fuels are hereby key, as a resource resupply will not be possible. Photoelectrochemical (PEC) devices are investigated for the light-assisted production of hydrogen and carbon-based fuels from CO2 within the green energy transition on Earth. Their monolithic design and the sole reliance on solar energy makes them attractive for applications in space. Here, we establish the framework to evaluate PEC device performances on Moon and Mars. We present a refined Martian solar irradiance spectrum and establish the thermodynamic and realistic efficiency limits of solar-driven lunar water-splitting and Martian carbon dioxide reduction (CO2R) devices. Finally, we discuss the technological viability of PEC devices in space by assessing the performance combined with solar concentrator devices and explore their fabrication via in-situ resource utilization.

Designing mixed-metal electrocatalyst systems for photoelectrochemical dinitrogen activation.

Efficient artificial photosynthesis systems are currently realized as catalyst- and surface-functionalized photovoltaic tandem-and triple-junction devices, enabling photoelectrochemical (PEC) water oxidation while simultaneously recycling CO2 and generating hydrogen as a solar fuel for storable renewable energy. Although PEC systems also bear advantages for the activation of dinitrogen - such as a high system tunability with respect to the electrocatalyst integration and a directly controllable electron flux to the anchoring catalyst through the adjustability of incoming irradiation - only a few PEC devices have been developed and investigated for this purpose. We have developed a series of photoelectrodeposition procedures to deposit mixed-metal electrocatalyst nanostructures directly on the semiconductor surface for light-assisted dinitrogen activation. These electrocatalyst compositions containing Co, Mo and Ru in different atomic ratios follow previously made recommendations of metal compositions for dinitrogen reduction and exhibit different physical properties. XPS studies of the photoelectrode surfaces reveal that our electrocatalyst films are to a large degree nitrogen-free after their fabrication, which is generally difficult to achieve with traditional magnetron sputtering or e-beam evaporation techniques. Initial chronoamperometric measurements of the p-InP photoelectrode coated with the Co-Mo alloy electrocatalyst show higher photocurrent densities in the presence of N2(g) than in the presence of Ar at -0.09 V vs. RHE. Indications of successful dinitrogen activation have also been found in consecutive XPS studies, where both N 1s and Mo 3d spectra reveal evidence of nitrogen-metal interactions.

Electrolysis in reduced gravitational environments: current research perspectives and future applications.

Electrochemical energy conversion technologies play a crucial role in space missions, for example, in the Environmental Control and Life Support System (ECLSS) on the International Space Station (ISS). They are also vitally important for future long-term space travel for oxygen, fuel and chemical production, where a re-supply of resources from Earth is not possible. Here, we provide an overview of currently existing electrolytic energy conversion technologies for space applications such as proton exchange membrane (PEM) and alkaline electrolyzer systems. We discuss the governing interfacial processes in these devices influenced by reduced gravitation and provide an outlook on future applications of electrolysis systems in, e.g., in-situ resource utilization (ISRU) technologies. A perspective of computational modelling to predict the impact of the reduced gravitational environment on governing electrochemical processes is also discussed and experimental suggestions to better understand efficiency-impacting processes such as gas bubble formation and detachment in reduced gravitational environments are outlined.

Fundamentals and future applications of electrochemical energy conversion in space.

Long-term space missions require power sources and energy storage possibilities, capable at storing and releasing energy efficiently and continuously or upon demand at a wide operating temperature range, an ultra-high vacuum environment and a significantly reduced buoyant force. Electrochemical energy conversion systems play already a major role e.g., during launch and on the International Space Station, and it is evident from these applications that future human space missions - particularly to Moon and Mars - will not be possible without them. Here, we will provide an overview of currently existing electrochemical conversion technologies for space applications such as battery systems and fuel cells and outline their role in materials design and fabrication as well as fuel production. The focus lies on the current operation of these energy conversion systems in space as well as the challenges posed on them by this special environment. Future experiment designs which could help elucidating and optimizing their key operating parameters for an efficient and long-term operation are discussed.

Magnetic phase separation in microgravity.

The absence of strong buoyancy forces severely complicates the management of multiphase flows in microgravity. Different types of space systems, ranging from in-space propulsion to life support, are negatively impacted by this effect. Multiple approaches have been developed to achieve phase separation in microgravity, whereas they usually lack the robustness, efficiency, or stability that is desirable in most applications. Complementary to existing methods, the use of magnetic polarization has been recently proposed to passively induce phase separation in electrolytic cells and other two-phase flow devices. This article illustrates the dia- and paramagnetic phase separation mechanism on MilliQ water, an aqueous MnSO4 solution, lysogeny broth, and olive oil using air bubbles in a series of drop tower experiments. Expressions for the magnetic terminal bubble velocity are derived and validated and several wall-bubble and multi-bubble magnetic interactions are reported. Ultimately, the analysis demonstrates the feasibility of the dia- and paramagnetic phase separation approach, providing a key advancement for the development of future space systems.

Releasing the Bubbles: Nanotopographical Electrocatalyst Design for Efficient Photoelectrochemical Hydrogen Production in Microgravity Environment.

Photoelectrochemical devices integrate the processes of light absorption, charge separation, and catalysis for chemical synthesis. The monolithic design is interesting for space applications, where weight and volume constraints predominate. Hindered gas bubble desorption and the lack of macroconvection processes in reduced gravitation, however, limit its application in space. Physico-chemical modifications of the electrode surface are required to induce gas bubble desorption and ensure continuous device operation. A detailed investigation of the electrocatalyst nanostructure design for light-assisted hydrogen production in microgravity environment is described. p-InP coated with a rhodium (Rh) electrocatalyst layer fabricated by shadow nanosphere lithography is used as a model device. Rh is deposited via physical vapor deposition (PVD) or photoelectrodeposition through a mask of polystyrene (PS) particles. It is observed that the PS sphere size and electrocatalyst deposition technique alter the electrode surface wettability significantly, controlling hydrogen gas bubble detachment and photocurrent-voltage characteristics. The highest, most stable current density of 37.8 mA cm-2 is achieved by depositing Rh via PVD through 784 nm sized PS particles. The increased hydrophilicity of the photoelectrode results in small gas bubble contact angles and weak frictional forces at the solid-gas interface which cause enhanced gas bubble detachment and enhanced device efficiency.

Experimental Methods for Efficient Solar Hydrogen Production in Microgravity Environment.

Long-term space flights and cis-lunar research platforms require a sustainable and light life-support hardware which can be reliably employed outside the Earth's atmosphere. So-called 'solar fuel' devices, currently developed for terrestrial applications in the quest for realizing a sustainable energy economy on Earth, provide promising alternative systems to existing air-revitalization units employed on the International Space Station (ISS) through photoelectrochemical water-splitting and hydrogen production. One obstacle for water (photo-) electrolysis in reduced gravity environments is the absence of buoyancy and the consequential, hindered gas bubble release from the electrode surface. This causes the formation of gas bubble froth layers in proximity to the electrode surface, leading to an increase in ohmic resistance and cell-efficiency loss due to reduced mass transfer of substrates and products to and from the electrode. Recently, we have demonstrated efficient solar hydrogen production in microgravity environment, using an integrated semiconductor-electrocatalyst system with p-type indium phosphide as the light-absorber and a rhodium electrocatalyst. By nanostructuring the electrocatalyst using shadow nanosphere lithography and thereby creating catalytic 'hot spots' on the photoelectrode surface, we could overcome gas bubble coalescence and mass transfer limitations and demonstrated efficient hydrogen production at high current densities in reduced gravitation. Here, the experimental details are described for the preparations of these nanostructured devices and further on, the procedure for their testing in microgravity environment, realized at the Bremen Drop Tower during 9.3 s of free fall.

Efficient solar hydrogen generation in microgravity environment.

Long-term space missions require extra-terrestrial production of storable, renewable energy. Hydrogen is ascribed a crucial role for transportation, electrical power and oxygen generation. We demonstrate in a series of drop tower experiments that efficient direct hydrogen production can be realized photoelectrochemically in microgravity environment, providing an alternative route to existing life support technologies for space travel. The photoelectrochemical cell consists of an integrated catalyst-functionalized semiconductor system that generates hydrogen with current densities >15 mA/cm2 in the absence of buoyancy. Conditions are described adverting the resulting formation of ion transport blocking froth layers on the photoelectrodes. The current limiting factors were overcome by controlling the micro- and nanotopography of the Rh electrocatalyst using shadow nanosphere lithography. The behaviour of the applied system in terrestrial and microgravity environment is simulated using a kinetic transport model. Differences observed for varied catalyst topography are elucidated, enabling future photoelectrode designs for use in reduced gravity environments.

Advancing semiconductor-electrocatalyst systems: application of surface transformation films and nanosphere lithography.

Photoelectrochemical (PEC) cells offer the possibility of carbon-neutral solar fuel production through artificial photosynthesis. The pursued design involves technologically advanced III-V semiconductor absorbers coupled via an interfacial film to an electrocatalyst layer. These systems have been prepared by in situ surface transformations in electrochemical environments. High activity nanostructured electrocatalysts are required for an efficiently operating cell, optimized in their optical and electrical properties. We demonstrate that shadow nanosphere lithography (SNL) is an auspicious tool to systematically create three-dimensional electrocatalyst nanostructures on the semiconductor photoelectrode through controlling their morphology and optical properties. First results are demonstrated by means of the photoelectrochemical production of hydrogen on p-type InP photocathodes where hitherto applied photoelectrodeposition and SNL-deposited Rh electrocatalysts are compared based on their J-V and spectroscopic behavior. We show that smaller polystyrene particle masks achieve higher defect nanostructures of rhodium on the photoelectrode which leads to a higher catalytic activity and larger short circuit currents. Structural analyses including HRSEM and the analysis of the photoelectrode surface composition by using photoelectron spectroscopy support and complement the photoelectrochemical observations. The optical performance is further compared to theoretical models of the nanostructured photoelectrodes on light scattering and propagation.

The protonation state around TyrD/TyrD• in photosystem II is reflected in its biphasic oxidation kinetics.

The tyrosine residue D2-Tyr160 (TyrD) in photosystem II (PSII) can be oxidized through charge equilibrium with the oxygen evolving complex in PSII. The kinetics of the electron transfer from TyrD has been followed using time-resolved EPR spectroscopy after triggering the oxidation of pre-reduced TyrD by a short laser flash. After its oxidation TyrD is observed as a neutral radical (TyrD•) indicating that the oxidation is coupled to a deprotonation event. The redox state of TyrD was reported to be determined by the two water positions identified in the crystal structure of PSII [Saito et al. (2013) Proc. Natl. Acad. Sci. USA 110, 7690]. To assess the mechanism of the proton coupled electron transfer of TyrD the oxidation kinetics has been followed in the presence of deuterated buffers, thereby resolving the kinetic isotope effect (KIE) of TyrD oxidation at different H/D concentrations. Two kinetic phases of TyrD oxidation - the fast phase (msec-sec time range) and the slow phase (tens of seconds time range) were resolved as was previously reported [Vass and Styring (1991) Biochemistry 30, 830]. In the presence of deuterated buffers the kinetics was significantly slower compared to normal buffers. Furthermore, although the kinetics were faster at both high pH and pD values the observed KIE was found to be similar (~2.4) over the whole pL range investigated. We assign the fast and slow oxidation phases to two populations of PSII centers with different water positions, proximal and distal respectively, and discuss possible deprotonation events in the vicinity of TyrD.

Bicarbonate-induced redox tuning in Photosystem II for regulation and protection.

The midpoint potential (Em) of [Formula: see text], the one-electron acceptor quinone of Photosystem II (PSII), provides the thermodynamic reference for calibrating PSII bioenergetics. Uncertainty exists in the literature, with two values differing by ∼80 mV. Here, we have resolved this discrepancy by using spectroelectrochemistry on plant PSII-enriched membranes. Removal of bicarbonate (HCO3-) shifts the Em from ∼-145 mV to -70 mV. The higher values reported earlier are attributed to the loss of HCO3- during the titrations (pH 6.5, stirred under argon gassing). These findings mean that HCO3- binds less strongly when QA-• is present. Light-induced QA-• formation triggered HCO3- loss as manifest by the slowed electron transfer and the upshift in the Em of QA HCO3--depleted PSII also showed diminished light-induced 1O2 formation. This finding is consistent with a model in which the increase in the Em of [Formula: see text] promotes safe, direct [Formula: see text] charge recombination at the expense of the damaging back-reaction route that involves chlorophyll triplet-mediated 1O2 formation [Johnson GN, et al. (1995) Biochim Biophys Acta 1229:202-207]. These findings provide a redox tuning mechanism, in which the interdependence of the redox state of QA and the binding by HCO3- regulates and protects PSII. The potential for a sink (CO2) to source (PSII) feedback mechanism is discussed.

Photocurrents from photosystem II in a metal oxide hybrid system: Electron transfer pathways.

We have investigated the nature of the photocurrent generated by Photosystem II (PSII), the water oxidizing enzyme, isolated from Thermosynechococcus elongatus, when immobilized on nanostructured titanium dioxide on an indium tin oxide electrode (TiO2/ITO). We investigated the properties of the photocurrent from PSII when immobilized as a monolayer versus multilayers, in the presence and absence of an inhibitor that binds to the site of the exchangeable quinone (QB) and in the presence and absence of exogenous mobile electron carriers (mediators). The findings indicate that electron transfer occurs from the first quinone (QA) directly to the electrode surface but that the electron transfer through the nanostructured metal oxide is the rate-limiting step. Redox mediators enhance the photocurrent by taking electrons from the nanostructured semiconductor surface to the ITO electrode surface not from PSII. This is demonstrated by photocurrent enhancement using a mediator incapable of accepting electrons from PSII. This model for electron transfer also explains anomalies reported in the literature using similar and related systems. The slow rate of the electron transfer step in the TiO2 is due to the energy level of electron injection into the semiconducting material being below the conduction band. This limits the usefulness of the present hybrid electrode. Strategies to overcome this kinetic limitation are discussed.

Wiring of Photosystem II to Hydrogenase for Photoelectrochemical Water Splitting.

In natural photosynthesis, light is used for the production of chemical energy carriers to fuel biological activity. The re-engineering of natural photosynthetic pathways can provide inspiration for sustainable fuel production and insights for understanding the process itself. Here, we employ a semiartificial approach to study photobiological water splitting via a pathway unavailable to nature: the direct coupling of the water oxidation enzyme, photosystem II, to the H2 evolving enzyme, hydrogenase. Essential to this approach is the integration of the isolated enzymes into the artificial circuit of a photoelectrochemical cell. We therefore developed a tailor-made hierarchically structured indium-tin oxide electrode that gives rise to the excellent integration of both photosystem II and hydrogenase for performing the anodic and cathodic half-reactions, respectively. When connected together with the aid of an applied bias, the semiartificial cell demonstrated quantitative electron flow from photosystem II to the hydrogenase with the production of H2 and O2 being in the expected two-to-one ratio and a light-to-hydrogen conversion efficiency of 5.4% under low-intensity red-light irradiation. We thereby demonstrate efficient light-driven water splitting using a pathway inaccessible to biology and report on a widely applicable in vitro platform for the controlled coupling of enzymatic redox processes to meaningfully study photocatalytic reactions.